Organic Letters
Letter
Nakamura, E. J. Am. Chem. Soc. 2013, 135, 17755. (d) Santhoshkumar,
R.; Mannathan, S.; Cheng, C.-H. J. Am. Chem. Soc. 2015, 137, 16116.
(5) For applications of (E)-1,2-diphosphinoethenes in coordination
chemistry, see: (a) Lozano, E.; Nieuwenhuyzen, M.; James, S. L. Chem.
- Eur. J. 2001, 7, 2644. (b) Brandys, M.-C.; Puddephatt, R. J. J. Am.
Chem. Soc. 2001, 123, 4839. (c) Brandys, M.-C.; Puddephatt, R. J. J.
Am. Chem. Soc. 2002, 124, 3946.
Scheme 6. Plausible Mechanism
(6) (a) Aguiar, A. M.; Daigle, D. J. Am. Chem. Soc. 1964, 86, 2299.
(b) Banert, K.; Fendel, W.; Schlott, J. Angew. Chem., Int. Ed. 1998, 37,
3289.
(7) Carty, A. J.; Johnson, D. K.; Jacobson, S. E. J. Am. Chem. Soc.
1979, 101, 5612.
(8) Kondoh, A.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2007,
129, 4099.
(9) Only native ethynyldiphenylphosphine underwent noncatalyzed
addition reaction with a lithium phosphide to form the corresponding
(E)-1,2-bis(diphenylphosphino)ethene: King, R. B.; Kapoor, P. N. J.
Am. Chem. Soc. 1971, 93, 4158.
(10) (a) Sato, A.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int. Ed.
2005, 44, 1694. (b) Kawaguchi, S.-i.; Nagata, S.; Shirai, T.; Tsuchii, K.;
Nomoto, A.; Ogawa, A. Tetrahedron Lett. 2006, 47, 3919.
(11) For noncatalyzed diphosphination of specially activated alkynes
including dimethyl acetylenedicarboxylate and methyl propiolate, see:
Dodds, D. L.; Haddow, M. F.; Orpen, A. G.; Pringle, P. G.;
Woodward, G. Organometallics 2006, 25, 5937.
(12) (a) Okugawa, Y.; Hirano, K.; Miura, M. Angew. Chem., Int. Ed.
2016, 55, 13558. (b) Unoh, Y.; Hirano, K.; Miura, M. J. Am. Chem. Soc.
2017, 139, 6106.
(13) (a) Rathman, T. L.; Schwindeman, J. A. Org. Process Res. Dev.
2014, 18, 1192. (b) Okano, K. Yuki Gosei Kagaku Kyokaishi 2017, 75,
364.
(14) No reaction occurred when diphenylacetylene was applied
under the standard conditions.
(15) (a) Romeo, R.; Wozniak, L. A.; Chatgilialoglu, C. Tetrahedron
Lett. 2000, 41, 9899. (b) Kondoh, A.; Yorimitsu, H.; Oshima, K. J. Am.
Chem. Soc. 2007, 129, 6996.
(16) The hydrogenation of the corresponding sulfide 3aa-S did not
occur under identical conditions using Pd(OH)2/C.
(17) Actually, we could not detect the alkynylphosphine during the
reaction of 1a with 2a in THF-d8 by 31P{1H} NMR analysis.
(18) Crystallographic data for the structure have been deposited with
the Cambridge Crystallographic Data Centre (CCDC 1544372). See
the Supporting Information for details.
phinoethene framework from terminal alkynes. Further
development of related phosphination reactions of unsaturated
molecules is ongoing and will be reported in due course.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
1H, 13C{1H}, 19F{1H}, and 31P{1H} NMR spectra and
Crystallographic data for 3ab-S (CIF)
AUTHOR INFORMATION
Corresponding Authors
■
ORCID
Notes
(19) Even under more forceful conditions (THF, 60 °C), the LiO-t-
Bu-mediated reaction of phenylacetylene (1a) with tetracyclohexyl-
diphosphane Cy2P−PCy2 formed the desired diphosphinated product
in only 15% 31P{1H} NMR yield.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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(20) We observed no remarkable change of 31P{1H} NMR signals of
diphosphanes (2a and 2b) even upon treatment with LiO-t-Bu in
THF-d8. Thus, base-promoted phosphorus scrambling is unlikely. See
This work was supported by JSPS KAKENHI Grant Nos. JP
15K13696 (Grant-in-Aid for Exploratory Research) and JP
15H05485 (Grant-in-Aid for Young Scientists (A)) to K.H. and
JP 24225002 (Grant-in-Aid for Scientific Research (S)) to
M.M. We thank Dr. Yuji Nishii (Osaka University) for his
assistance of X-ray analysis.
scheme.
(22) Unfortunately, we could not observe the intermediate 7 in 31P
NMR analysis. Additionally, the addition of TEMPO and galvinoxyl
completely shut down the reaction. Thus, we cannot exclude the
possibility of the radical pathway.
REFERENCES
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(1) (a) Cadogan, J. I. G. Organophosphorus Reagents in Organic
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(2) (a) Metal-Catalyzed Cross-Coupling Reactions; de Meijere, A.,
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Chem., Int. Ed. 2002, 41, 1998. (c) Noyori, R. Angew. Chem., Int. Ed.
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́
(3) For selected examples, see: (a) Baumgartner, T.; Reau, R. Chem.
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1613.
(4) For recent applications of (Z)-1,2-diphosphinoethenes in
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Am. Chem. Soc. 2010, 132, 6935. (b) Ghosh, A. K.; Kass, J.; Nicponski,
D. R.; Keyes, C. Synthesis 2012, 44, 3579. (c) Asako, S.; Ilies, L.;
D
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